Ternäre Halogenide vom Typ A3MX6. VI [1]. Ternäre Chloride der Selten-Erd-Elemente mit Lithium,Li3MCl6 (M  Tb?Lu,Y, Sc): Synthese,Kristallstrukturen und Ionenbewegung

Ternary Halides of the A₃MX₆ Type. VI. Ternary Chlorides of the Rare-Earth Elements with Lithium, Li₃MCl₆ (M ? Tb? Lu, Y, Sc): Synthesis, Crystal Structures, and Ionic Motion Single crystal X-ray studies on the ternary chlorides Li₃ErCl₆, Li₃YbCl₆ and Li₃ScCl₆ show that they crystallize in three different structure types. Li₃ErCl₆ (trigonal, P3 ml, Z = 3, a = 1117.7(2); c = 603.6(2) pm; the chlorides with M ? Tb? Tm, Y are isotypic) and Li₃YbCl₆ (orthorhombic, Pnma, Z = 4, a = 1286.6(1); b = 1113.2(1); c = 602.95(8) pm; Li₃LuCl₆ is isotypic) have very similar structures that may be derived from hexagonal closest packings of chloride ions with the cations occupying octahedral holes in part statistically. Li₃ScCl₆ (monoclinic, C2/m, Z = 2, a = 639.8(1); b = 1104.0(2); c = 639,1(1) pm; β = 109.89(1)°) crystallizes isotypic with Na₃GdI₆ and Li₃ErBr₆, structures that may be derived from a cubic closes packings of anions. The ionic movement in Li₃YCl₆ and Li₃YbCl₆ has been investigated by impedance and ⁷Li-NMR spectroscopy.     

Synthesen und Charakterisierungen der ersten Tris‐ und Tetrakis(trifluormethyl)palladate(II) und ‐platinate(II), [M(CF3)3(PPh3)]— und [M(CF3)4]2— (M = Pd,Pt)

Syntheses and Characterizations of the First Tris and Tetrakis(trifluoromethyl) Palladates(II) and Platinates(II), [M(CF₃)₃(PPh₃)]^— and [M(CF₃)₄]^2— (M = Pd, Pt) Tris(trifluoromethyl)(triphenylphosphino)palladate(II) and platinate(II), [M(CF₃)₃PPh₃]^—, and the tetrakis(trifluoromethyl)metallates, [M(CF₃)₄]^2— (M = Pd, Pt), are prepared from the reactions of [MCl₂(PPh₃)₂] and Me₃SiCF₃ / [Me₄N]F or [I(CF₃)₂]^— salts in good yields. [Me₄N][M(CF₃)₃(PPh₃)] crystallize isotypically in the orthorhombic space group Pnma (no. 62) with Z = 4. The NMR spectra of the new compounds are described.     

Comment on the Paper: “Crystal Structure of the Bis[zinc(II)‐hydroxide‐(μ‐perchlorate‐triaqua] Complex” by Y.‐H. Li,Q. Ye,Y.‐Z. Tang,and R.‐G. Xiong (Z. Anorg. Allg. Chem. 2004, 630, 1553)

In the present comment it will be outlined that the recently published perchlorate [Zn(OH)(μ‐ClO₄)(H₂O)₃]₂ is in fact the well known sulfate ZnSO₄·4H₂O. The assumption is supported by both bond lengths considerations and structural characteristics.     

Polysulfates [SnO3n+1]2−: With the [S6O19]2− Anion,has the End been Reached?

The S₆O₁₉^2? ion was obtained both as rubidium and ammonium salt from the reaction of the respective sulfate with SO₃. It is the largest polysulfate ion known to date and exhibits a chain of six vertex‐connected [SO₄] tetrahedra. The unique compound was comprehensively characterized and the bonding within the anion was elucidated by theoretical investigations.     

Palladium(IV) in an Oxoanionic Environment: The XeF2 Assisted Synthesis of [Pd(S2O7)3]2−

For the first time tetravalent palladium is detected, coordinated exclusively by simple oxoanions. Stabilization was achieved by formation of the [Pd(S₂O₇)₃]^2? complex in which three chelating disulfate groups surround the metal atom. The salt K₂[Pd(S₂O₇)₃] could only be obtained if the reaction of K₂[PdCl₆] and neat SO₃ was performed in the presence of XeF₂.     

A Highly Triflated Rare‐Earth Ion in [Eu(O3SCF3)8]5−

The reaction of Eu₂O₃ with fuming nitric acid, trifluormethanesulfonic acid, and its anhydride in torch‐sealed glass ampoules at 120 °C gave the europium compound (NO)₅[Eu(O₃SCF₃)₈] (orthorhombic, Fddd, Z=16, a=1932.69(4), b=2878.44(7), c=2955.12(7) pm, V=16439.7(7) ų). The compound exhibits the [Eu(O₃SCF₃)₈]^5? anion showing for the first time a lanthanide ion that is exclusively coordinated by eight triflate anions. The anion has been further investigated by DFT calculations, which also allowed clear assignment of the vibrational spectra. Moreover, magnetochemical and luminescence measurements gave additional insight into the properties of this complex. The luminescence spectra revealed that the Eu³⁺ ions are in a pseudo D_4d symmetric environment.